Continuous chlorine dioxide generation

ABSTRACT

The present invention provides a system for continuously and efficiently producing low concentrations of aqueous chlorine dioxide from a dilute continuous feed stream of aqueous chlorite.

RELATED APPLICATIONS

The present invention is a first Divisional (via RestrictionRequirement, Original Claims 1-10) of U.S. patent application Ser. No.10/730,730, filed Dec. 8, 2003, entitled “CONTINUOUS CHLORINE DIOXIDEGENERATION,” now, U.S. Pat. No. ______. Concurrently, a secondDivisional (via Restriction Requirement, Original Claims 24-30), isbeing filed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the continuous and efficient productionof low concentrations of aqueous chlorine dioxide from a dilutecontinuous feed stream of aqueous chlorite.

2. Description of the Related Art

Chlorine dioxide, ClO₂, is a greenish yellow gas with an appreciablesolubility in water. It is a powerful, yet selective, oxidant that cankill fungi, bacteria and algae in a variety of applications, among whichare the treatment of drinking water, the processing of wastewater, thedisinfection of fruit and vegetables, the processing of poultry, and thecontrol of microbiological growth in cooling towers. The benefit ofchlorine dioxide as compared to other oxidizing agents in this class,such as chlorine, is that chlorine dioxide's use does not generateunwanted and perhaps hazardous chlorinated organic byproducts. Chlorinedioxide is a powerful oxidizing agent that is readily soluble in water.In its pure gaseous state, it is unstable and cannot be compressed,shipped or stored. Accordingly, chlorine dioxide must be generated atthe point of use.

Chlorine dioxide can be generated from a variety of chlorine-containingstarting compounds including various salts of the oxychlorine anionssuch as chlorite and chlorate. The chlorite ion readily reacts withacids or chlorine to form ClO₂. Ultraviolet irradiation of aqueoussolutions containing the chlorite ion will also generate chlorinedioxide.

Due to the nature of chlorine dioxide, it must be created or generatedat the point of consumption or use. Commercially viable technologieshave limited its use to applications where generally quantities greaterthan 5 pounds per day of chlorine dioxide are required.

U.S. Pat. No. 4,414,180 and U.S. Pat. No. 4,456,511 disclose a methodfor generating chlorine dioxide gas by metering nitrogen or air directlyinto a generator containing aqueous sodium chlorite, and illuminating byone or more incandescent or fluorescent lamps. The sodium chlorite isphotochemically oxidized to chlorine dioxide and the resulting chlorinedioxide is taken into the gas phase by the nitrogen or air gas stream.

U.S. Pat. No. 4,874,489 to Callerame (1989) discloses generating a batchof chlorine dioxide by subjecting chlorite to ultraviolet radiation. Thechlorine dioxide can easily be displaced from the reaction with air anddissolved in water to form chlorous acid.

U.S. Pat. No. 6,171,558 discloses a chlorine dioxide generator for usewith a container holding aqueous chlorite. The apparatus includes a lampfor generating radiation, a connector or cap attached to the lamp sothat the lamp is positioned within the container, and a circulation tubeproximate to the light for circulating the aqueous chlorite in contactwith the lamp radiation to create chlorine dioxide. Finely divided gasbubbles sweep microbubbles of chlorine dioxide upwardly from theexterior surface of the quartz housing through exit apertures and thenceto the field of use. After the aqueous chlorite solution is depleted,the ultraviolet portion of the generator can be removed and reinstalledin a new container of aqueous chlorite, or moved to another location.

For each of the above noted patents, (despite assertions in U.S. Pat.No. 6,171,558) the chlorine dioxide is produced in a batch process and agas is used to sweep the chlorine dioxide as a gas from the generatorvessel.

There are a number of shortcomings with the prior art devices andmethods for producing chlorine dioxide by irradiating an aqueouschlorite:

-   -   1. Batch processes compared with continuous processes inherently        require more equipment and higher cost.    -   2. Removing the chlorine dioxide as a gas significantly reduces        the efficiency which can be obtained.    -   3. With a batch process, the pH typically increases above 10        resulting in lower conversion of chlorite to chlorine dioxide.    -   4. With a batch process, the heat from the lamp(s) is not        dissipated resulting in a higher lamp operating temperature with        a lower ultraviolet wattage output.    -   5. With a batch process, there exists significant photolytic        decomposition of the product chlorine dioxide resulting in a low        conversion of chlorite to chlorine dioxide.    -   6. With a batch process, there exists significant unwanted side        reactions that produce unwanted by-products and reduce the        conversion efficiency.

SUMMARY OF THE INVENTION

Accordingly, a need exists for a system to safely, reliably andeconomically produce chlorine dioxide in an aqueous solution on acontinuous basis in small quantities (up to about 5 pounds per day ofchlorine dioxide). The low concentration continuous feed system of thepresent invention solves several problems associated with prior arttechnologies.

-   -   1. The system is truly continuous unlike assertions in prior art        patents. The system continuously feeds a low concentration        chlorite solution and produces a continuous stream of chlorine        dioxide solution.    -   2. Explosion hazards associated with high concentrations of        chlorine dioxide are avoided by operating at low concentrations        well below the danger level.    -   3. With a continuous low concentration system, the pH is kept        below 10 allowing higher conversion to chlorine dioxide.    -   4. The continuous flow provides cooling to the lamps maintaining        the lamp temperature in the highest output ranges.    -   5. The continuous flow system adds to the higher efficiency by        minimizing the subsequent photolytic decomposition of the        product chlorine dioxide.    -   6. The low concentration regime minimizes unwanted side        reactions that produce unwanted by-products and reduce the        efficiency of the system.

The present invention provides feeding a stream of aqueous sodiumchlorite or other aqueous alkali metal or alkaline earth metal chloritein concentrations between about 0.001% to about 0.25% to a reactingvessel where the sodium chlorite is irradiated with ultraviolet light toform a product stream that has between about 0.0005% and about 0.05%chlorine dioxide in solution under continuous flow. An important featureof this invention is obtaining high conversion efficiencies of chloriteto chlorine dioxide. This is accomplished by combining a lowconcentration chlorite feed solution with proper lamp arrangement andspacing and flow distribution to attain a conversion efficiency ofbetween 20% and 43% of chlorite to chlorine dioxide on a sustainedbasis.

Because of the efficacy of chlorine dioxide as a disinfectant, biocideor selective oxidant, potential applications or markets exist forchlorine dioxide in small quantities of up to about 5 pounds per day. Toreach these potential markets, the chlorine dioxide and its generationmust be (1) cost effective, (2) safe, (3) easy to use and (4) reliable.Since potential precursor chemicals involved in chlorine dioxidegeneration are relatively expensive and unreacted precursor chemical andreaction by-products can be of concern, the efficiency of the generationsystem is important. The prior art technologies have not successfullyaddressed these issues.

BRIEF DESCRIPTION OF THE DRAWINGS

A better understanding of the invention can be obtained when thedetailed description of exemplary embodiments set forth below isconsidered in conjunction with the attached drawings in which:

FIG. 1 is a graph of mM Comparison with Residence Time.

FIG. 2 is a simplified drawing of the overall system of the presentinvention.

FIG. 3 is a simplified drawing of an alternate feed system for use withthe present invention.

FIG. 4 a is a plan view of the distributor plate of the presentinvention.

FIG. 4 b is an elevation view of the distributor plate of the presentinvention.

FIG. 5 is a simplified drawing of the reacting vessel of the presentinvention.

DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS

The present invention provides a system to produce chlorine dioxide bypreparing a feed stream containing about 0.001 wt % to about 0.25 wt %sodium chlorite and with proper feed distribution and configuration,passing the feed stream past ultraviolet radiation in a manner thatconverts between about 20 wt % and about 43 wt % of the chlorite tochlorine dioxide. The feed and product streams are continuous.

FIG. 1 shows one of the typical experimental results comparing theconcentration of the feed chlorite (ClO₂ ⁻), the chlorine dioxide (ClO₂)produced, the chloride (Cl⁻) produced and the chlorate (ClO₃ ⁻)apparently produced all expressed in milli-molar (mM) quantities versusthe exposure to ultraviolet light expressed as minutes of residence timeof the solution in the reacting vessel. The feed solution had 1000 partsper million (ppm) sodium chlorite and the reacting vessel contained fivelamps producing a total of 55 watts of ultraviolet radiation.

It is known that ultraviolet radiation will cause a photochemicalreaction with chlorite forming chlorine dioxide and also that theultraviolet radiation will cause the destruction of the chlorinedioxide. Previous work and patents were based on the assumption that inorder to recover the chlorine dioxide before it is subsequentlydestroyed, the chlorine dioxide must be removed from the ultravioletradiation source as quickly as possible. Through many experimentaltrials, it is believed that the reaction producing chlorine dioxide fromchlorite will preferentially absorb the ultraviolet radiation and onlywhen there is not chlorite available will the ultraviolet radiation thendecompose the chlorine dioxide. This is particularly true when thechlorite feed solution is very dilute and the flow is properlydistributed past the ultraviolet source.

From making and observing many test runs using different combinations offactors, it was observed that when a chlorite solution is irradiatedwith ultraviolet light produced by a mercury vapor lamp, chlorinedioxide and chloride ions are produced (simplified as reaction #1). Thedata seems to indicate that the reactions are linked as the chlorinedioxide and chloride ions are produced in approximately equal molarquantities throughout the initial stages of the reaction. The reactionprogresses until all of the chlorite is consumed. A further photolyticprocess converts chlorine dioxide into chlorate ions under the mildlybasic conditions employed here (simplified as reaction #2). It isbelieved that this reaction does not produce chloride ions and does notoccur to an appreciable extent until the available chlorite is equal toor less than the chlorine dioxide concentration. Once the chlorite isconsumed, the chloride ion concentration remains constant, the chlorinedioxide decreases to zero and the apparent chlorate concentration rises.The complete mechanism by which these reactions occur is not fullyunderstood. The most detailed work in this field was done by Buxton andSubhani in 1971 using flash photolysis techniques and does not explainthe time effect seen in this study. Their work predicted that OCl⁻ isformed or possibly involved in these reactions. A test was run byapplicants where a weak OCl⁻ solution was irradiated with theultraviolet light source without any ClO₂ ⁻ being present. The OCl⁻concentration was measured before irradiation and after and showed analmost complete disappearance of the OCl⁻. The chloride (Cl⁻) was alsomeasured before and after and there was no change in the concentration.The titration for OCl⁻ would have also indicated the presence of Cl₂ orClO₂, which also were not indicated, leading to the conclusion that theOCl⁻ was probably being converted to ClO₃ ⁻. Reaction #2 from abovecould actually be going through an OCl⁻ step based on this test. Thereactions likely involve electron transfer as well as oxygen-containingspecies such as OH⁻ ions, O atoms and O⁻ radical anions. Since thereactions occur in a very dilute aqueous solution and the chlorite isinitially in the form of sodium (or other alkali metal) chlorite,hydroxide ion and hydrogen are likely formed. The pH was recordedextensively during the various test runs and the pH rises as chloritereacts but reaches a maximum that is usually less than a 1.5 pH unitshigher than the initial pH. The pH then begins to decline. The pH willeventually reach the initial value and can go below if the reaction isrun to achieve complete conversion of chlorine dioxide into chlorateion. In the test irradiating OCl⁻, the beginning pH was 8.17 and droppedto 7.55 after irradiation.

It is preferred that the ultraviolet radiation used is produced in lampsthat use low-pressure mercury vapor and produce radiation of primarily254 nanometers (nm) but also produce smaller amounts of radiation at 185nm and 315 nm. The preferred lamps produce ultraviolet radiation inexcess of 0.8 ultraviolet watts per inch of arc in the lamp. Theradiation at 185 nm is also known to produce ozone. The inclusion of the185 nm radiation in this chlorine dioxide system improved the efficiencyby up to 2%. This could be the result of the photolysis of chlorite atthe 185 nm or the reaction of ozone produced at that wavelength with thechlorite forming chlorine dioxide.

One of the important elements in this system is balancing the amount ofchlorite being fed with the available ultraviolet radiation. The numberand type of lamps being used and the ballast that drives them fix theamount of ultraviolet radiation available. The chlorite being fed shouldcorrelate with the available ultraviolet radiation. For peakefficiencies, between 0.012 and 0.082 pounds of chlorite (Cl₂ ⁻) shouldbe fed to the system each day for each watt of ultraviolet radiationapplied. The feed preferably contains between 0.001% and 0.25% chloritein water solution. Sodium chlorite is available commercially in watersolution in strengths from 7.5% to 35% any of which can be used inpreparing the feed stream by further diluting with water. In thisinvention, this is done on a continuous basis by either pumping therequired chlorite into a controlled water stream or using the waterstream to motivate an eductor to educt the required chlorite intosolution.

FIG. 2 shows the overall system 10 of the present invention. A source ofwater feeds the system 10 through the water feed line 11. A flow controldevice, shown as a rotameter 12 having a valve 13, is used to controlthe flow of water. A source of chlorite feeds the system 10 through thechlorite feed line 14. A flow control device, shown as a rotameter 15having a valve 16, is used to control the flow of chlorite. Any suitableflow measurement and flow control devices may be used. An eductor 17 isused to educt the chlorite into the water stream producing a dilutechlorite solution 18 preferably containing between about 0.001 wt % andabout 0.25 wt % chlorite. The dilute chlorite solution 18 is fed to thereacting vessel 19, preferably in a lower part of the reacting vessel19. The reacting vessel 19 contains one or more UV lamps 20 a (see FIG.5) enclosed within one or more quartz or fluoropolymer plastic (e.g.,TEFLON) tubes 20, a distributor plate 21, and a holding plate 22. Thedistributor plate 21 serves to distribute the flow of the dilutechlorite solution 18 such that the dilute chlorite solution 18 will flowin an evenly distributed flow near the one or more UV lamps 20 a. Theholding plate 22 serves to hold the UV lamps 20 a within the reactingvessel 19. The product stream 24 flows out the reacting vessel 19through the exit nozzle 23. The system 10 produces a product stream 24having a chlorine dioxide concentration of between about 0.0005 wt % andabout 0.05 wt %.

FIG. 3 shows an alternate feed system 30. The water feed line 11 isrouted to a valve 31 which is used to control the water flow rate. Thechlorite is provided to the feed system 30 through the chlorite feedline 14. The chloride is pumped with pump 32 into the water stream toproduce the dilute chlorite solution 18.

Generally, the feed systems shown in FIG. 2 is preferred because, if theflow rate of water stops with the FIG. 2 embodiment, the eductor 17 willnot operate to educt the chlorite into the system 10. If the water flowrate stops and a high concentration of chlorite is irradiated with theUV lamps (generally, more of a possibility with the FIG. 3 embodiment),then there exists the possibility that high concentration of chlorinedioxide could be generated which would cause an explosion hazard.

Additional details regarding the reacting vessel 19 are shown in FIGS. 4a, 4 b, and 5. Preferably, the feed stream enters the reacting vessel atthe bottom and passes through the distributor plate 21 shown in FIGS. 4a and b. It is preferred to evenly distribute the flow past theultraviolet radiation. The distributor plate 21 includes a number oflarger holes 25 designed to mate with the quarts or fluoropolymerplastic tubes 20 which holds the UV lights 20 a and a number of smallerholes 26 designed to evenly distribute the dilute chlorite solution 18within the reacting vessel 19. The reacting vessel 19 assembly shown inFIG. 5 contains six lamps 20 a with an arc length of 28 inches. Thereacting vessel 19 has an inside diameter of 4 inches. The lamps 20 aare inside quartz or fluoropolymer plastic tubes 20 in the reactingvessel 19. The lamps are geometrically configured to fit inside a 4 inchdiameter reacting vessel 19. The quartz or fluoropolymer plastic tubes20 protrude through and are sealed at the top of the holding plate 22.This allows the electrical connection to be made outside the liquidinside the reacting vessel 19. The quartz or fluoropolymer plastic tubes20 are secured at the bottom of the reacting vessel 19 via thedistributor plate 21. A pipe cap (not shown) is used to enclose thebottom end of the reacting vessel 19. The distributor plate 21 may bemade from ¼ inch thick PVC. The reaction vessel 19 is best operated inthe vertical position but will work in any position at a loss ofefficiency.

The amount of available ultraviolet radiation is determined by the type,size and number of lamps 20 a used. The distribution of the flow pastthe lamps 20 a and the spacing of the flow around the lamps 20 a affectthe conversion efficiency of the chlorite to chlorine dioxide. The flowof the feed solution should be no more than 0.75 inches from a lamp 20 aas it passes through the reacting vessel 19. The system is not dependenton the length of the lamps 20 a and works equally well with differentarc lengths in the lamps 20 a. With a system with multiple lamps 20 a,preferably the lamps 20 a are spaced in a cluster such that there arenot areas where the dilute chlorite solution 18 can form a channel andflow past the lamps 20 a without being completely irradiated. Theproduct stream 24 exits the reacting vessel 19 at the top through theexit nozzle 23 after the dilute chlorite stream 18 has passed all of theavailable arc length of the ultraviolet lamps 20 a. This assures thatthe lamps 20 a, surrounded by the quartz or fluoropolymer plastic tubes20, are always immersed or flooded with liquid. The low of dilutechlorite solution 18 through the reacting vessel 19 is continuousproducing a continuous product stream 24. The lamps 20 a generate heat.The flow of the dilute chlorite solution 18 through the reacting vessel19 provides cooling for the lamps 20 a and maintains the temperature atwhich the lamps are operating at below 120° F. keeping them operatingefficiently. Without this cooling effect, the lamps could heat totemperatures where the ultraviolet output is greatly diminished.

Not only does the low concentration of chlorite in the dilute chloritestream 18 provide for best conversion efficiency, it also eliminates thepossibility that the concentration of chlorine dioxide produced in theproduct stream 24 can reach unsafe levels. Previous systems andtechnology used higher concentrations of chlorite that was reacted as abatch without continuous input and discharge. In these systems, thechlorine dioxide was removed from the reaction chamber by stripping itout as a gas with air or other inert gas. To keep the solution near thelamps, circulation tubes were used around the quartz tubes and lamps.This invention does not require any gas stripping or internalcirculation. This invention produces a continuous stream of chlorinedioxide in water solution.

The present inventive system is advantageous over known chlorine dioxidegenerators. The present invention provides a safe, reliable, continuouschlorine dioxide product stream 24 having a low concentration ofchlorine dioxide (about 0.0005 wt % to about 0.05 wt %) which issuitable for a number of applications such as the treatment of drinkingwater, the processing of wastewater, the disinfection of fruits andvegetables, the processing of poultry, and the controlling ofmicrobiological growth in cooling towers.

All patents and publications referred to herein are hereby incorporatedby reference in their entireties.

Having described the invention above, various modifications of thetechniques, procedures, materials, and equipment will be apparent tothose skilled in the art. It is intended that all such variations withinthe scope and spirit of the invention be included within the scope ofthe appended claims.

1. A method for producing a continuous aqueous solution of chlorinedioxide comprising the steps of: a obtaining an aqueous alkali metal oralkaline earth metal chlorite solution having up to about 35 wt % of thealkali metal or alkaline earth metal chlorite, b. with water, dilutingthe aqueous alkali metal or alkaline earth metal chlorite to form acontinuous feed stream having a chlorite concentration of between about0.001 wt % and about 0.25 wt %, c. irradiating the continuous feedstream in a reacting vessel with ultraviolet light radiation, and d.producing a continuous aqueous product stream containing between about0.0005 wt % and about 0.05 wt % chlorine dioxide.
 2. The method of claim1, wherein the aqueous alkali metal or alkaline earth metal chlorite issodium chlorite.
 3. The method of claim 1, wherein the continuous feedstream is irradiated in a reacting vessel with ultraviolet radiationhaving primary wavelengths of 254 nm.
 4. The method of claim 1, whereinthe continuous feed stream reacts in the presence of the ultravioletradiation to form primarily chlorine dioxide, chloride and chlorate. 5.The method of claim 1, wherein the continuous feed stream containsbetween about 0.00052 pound of chlorite to about 0.0034 pound ofchlorite for each watt·hr of ultraviolet radiation applied.
 6. Themethod of claim 1, wherein the chlorite in the continuous feed stream isconverted by 20 wt % to 43 wt % to chlorine dioxide.
 7. The method ofclaim 4, wherein the chlorite in the continuous feed stream reactspreferentially to form chlorine dioxide and chloride in approximatelyequal molar quantities.
 8. The method of claim 1, wherein the productstream has a pH in the alkaline range.
 9. The method of claim 1, whereinthe product stream has a pH between 9.0 and 9.7.
 10. The method of claim1, wherein the product stream has a pH less than 10.